US4246292A - Substituted cyclohexanones as flavor materials - Google Patents

Substituted cyclohexanones as flavor materials Download PDF

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Publication number
US4246292A
US4246292A US05/853,907 US85390777A US4246292A US 4246292 A US4246292 A US 4246292A US 85390777 A US85390777 A US 85390777A US 4246292 A US4246292 A US 4246292A
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United States
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hydrogen
groups
compound
weight
parts
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Expired - Lifetime
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US05/853,907
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English (en)
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Wilhelmus M. B. Konst
Roelof ter Heide
Hendrik J. Wobben
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Naarden International NV
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Naarden International NV
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B9/00—Essential oils; Perfumes
    • C11B9/0026—Essential oils; Perfumes compounds containing an alicyclic ring not condensed with another ring
    • C11B9/0034—Essential oils; Perfumes compounds containing an alicyclic ring not condensed with another ring the ring containing six carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C403/00—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone
    • C07C403/02—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains containing only carbon and hydrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/28—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of CHx-moieties
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/62—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by hydrogenation of carbon-to-carbon double or triple bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/78—Separation; Purification; Stabilisation; Use of additives
    • C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
    • C07C45/82—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated

Definitions

  • This invention deals with substituted cyclohexenones and cyclohexanones with a structure according to the general formula 1, shown in the accompanying formulae drawings, wherein R 1 , R 2 , R 3 , R 4 and R 5 may be the same or different and are H or methyl groups, the dotted lines indicate possible double bonds, provided that the side chain carrying R 4 and R 5 contains not more than one double bond, and R 6 means hydrogen or a methyl or ethyl group when no double bond to R 6 is present, or a methylene or ethylidene group when a double bond to R 6 is present.
  • Several alkyl substituted cyclohexenones are known to be useful as flavour or fragrance compounds.
  • the compounds of this invention have not been described before and are structurally very different from the compounds of the above cited prior art. They lack the side chain functional group of the compounds of U.S. Pat. No. 3,746,010 and DOS No. 2,353,468 on one hand and have the keto group and the ring double bond in a different position compared with the compounds of French patent No. 1,533,234 on the other hand.
  • flavour and fragrance materials are those compounds wherein R 1 stands for hydrogen and wherein only one of R2, R3, R4 and R5 is methyl, the others being hydrogen. Especially preferred are the compounds wherein R2, R3, R4 and R5 are all hydrogen.
  • the compounds of the invention may be used as such as aroma or fragrance materials, or they may first be combined with carriers or diluents. They may also be compounded with other single compounds or mixtures (e.g. essential oils) in a manner conventional in the art to form aroma or perfume compositions.
  • aroma perfume composition
  • auxiliary materials dissolved in a suitable solvent or mixed with a suitable powdery substrate if desired, and used to impart a desirable flavour (odour) to various kinds of products, or strengthen the flavour (odour) they already have.
  • Examples of products to be flavoured are: foodstuffs, beverages including alcoholic drinks, tobacco, pharmaceuticals, etc.
  • Products and articles to be perfumed are e.g. soaps, detergents, cleaners, room deodorants, cosmetic creams, ointments and other cosmetic products, etc.
  • the amounts of the compounds to be used according to the invention may vary widely and depends strongly on what product the flavour and fragrance compounds of this invention are used in. It also depends on the type and quantity of the other components in an aroma or perfume composition and on the desired type and strength of the aroma or perfume composition.
  • reaction scheme A In concentrated perfume compositions quantities of only 0.05% by weight will generally have a clearly perceptible effect on the odour impression, but also quantities of up to 10% may be used for purposes requiring a strong odour impact. In products perfumed with compositions containing the compounds of this invention, the quantities of these compounds may be much lower, depending on the quantity of the composition that has been incorporated in the product.
  • the compounds of this invention may be prepared according to the reaction sequences outlined in reaction scheme A and B of the formulae drawings. These reaction schemes are given for the specific case that R 1 ⁇ R 2 ⁇ R 3 ⁇ R 4 ⁇ R 5 ⁇ H and R 6 is methyl or methylene but apply also to the synthesis of the other compounds of this invention. Reaction scheme A starts with ⁇ or ⁇ damascone or its homologues, whereas reaction scheme B starts with ⁇ or ⁇ ionone, but also applies to the corresponding irones and methylionones and their homologues.
  • Ionone homologues suitable as starting compounds in reaction scheme B may be prepared from citral homologues obtained according to British Patent No. 1,305,621 and literature cited therein.
  • a solution of 192 g of ⁇ -ionone in 1 L of ethanol is subjected to catalytic hydrogenation at 10 ato and 100° C. using 2% Nickel catalyst.
  • the catalyst is subsequently filtered off.
  • the resulting dihydro- ⁇ -ionone is reduced in 4 hours at 5°-10° C. with 14 g NaBH 4 dissolved in ethanol.
  • the resulting reaction mixture is acidified with acetic acid to pH 4.
  • the solvent is distilled off under reduced pressure. 250 ml of water is added and the mixture is extracted 3 times with ether.
  • the etheral solution is dried over Na 2 SO 4 and the ether removed by evaporation. The residue is distilled under reduced pressure.
  • the compounds could be separated by gaschromatography over a 2 m column 10% DEGS at 175° C.
  • the cis-but-2'-en-1'-yl compound has a strong raspberry odour with a distinct woody and a less pronounced celery note.
  • the trans compound has the same odour character although somewhat weaker.
  • the but-3'-en-1'-yl compound has a less pronounced raspberry odour but possesses a more flowery rose-like character.
  • the compound has a sweet fruity odour also reminding of vanillin, with distinct woody and cellery-like notes.
  • the mixture has a strong fruity (raspberry) and flowery odour with a woody and a weak tobacco-like note.
  • ⁇ -Isomethylionone was directly hydrogenated to dihydro-isomethylionol at 130° C. and 10 ato using 2% Nickel catalyst.
  • the resulting compound was dehydrated in hexamethylphosphorous triamide and oxidized with tert.butylchromate as described in example 1 to yield a mixture of the title compounds, which could be separated gaschromatographically.
  • the mixture has a fresh fruity and rose-like odour.
  • the compound has a sweet fruity odour, with distinct woody, herbal and hay-like note.
  • a standard raspberry flavour composition was prepared according to the following recipe:
  • flavour concentrate Another ready to use flavour concentrate was prepared by adding 100 mg of the mixture of compounds obtained in example 1 to 1000 g of a flavour concentrate obtained as described above. Carbonated beverages were prepared from both flavour concentrates using 1 g of the flavour concentrate for each liter of finished beverage.
  • a standard apple flavour composition was prepared according to the following recipe:
  • flavour concentrate was prepared by adding 1 g of the compound obtained according to example 3 to 1000 g of the flavour concentrate obtained as described above.
  • Carbonated beverages were prepared from both flavour concentrates using 1 g of the concentrate for each liter of finished beverage.
  • a triangle test 8 out of 10 persons had a clear preference for the beverage with the compound of the invention for having a more rounded off apple flavour.
  • An aftershave perfume concentrate was prepared according to the following recipe:
  • a creme perfume concentrate was prepared according to the following recipe:
US05/853,907 1976-11-23 1977-11-22 Substituted cyclohexanones as flavor materials Expired - Lifetime US4246292A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB48762/76 1976-11-23
GB48762/76A GB1591098A (en) 1976-11-23 1976-11-23 Substituted cyclohexanones as falvour and fragrance materials

Publications (1)

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US4246292A true US4246292A (en) 1981-01-20

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US05/853,907 Expired - Lifetime US4246292A (en) 1976-11-23 1977-11-22 Substituted cyclohexanones as flavor materials

Country Status (7)

Country Link
US (1) US4246292A (de)
JP (1) JPS5368754A (de)
CH (1) CH633508A5 (de)
DE (1) DE2752787A1 (de)
FR (1) FR2371412A1 (de)
GB (1) GB1591098A (de)
NL (1) NL7712928A (de)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4311718A (en) * 1977-03-28 1982-01-19 Givaudan Corporation Flavoring with 2,4,4-trimethyl-3-(buta-1,3-dienyl)cyclohex-2-en-one
US4326997A (en) * 1980-10-08 1982-04-27 Fritzsche Dodge & Olcott Inc. Fragrance compositions of alicyclic ketone and alcohol derivatives
US4326996A (en) * 1980-01-30 1982-04-27 Fritzsche Dodge & Olcott Inc. Fragrance composition comprising substituted cyclohexane derivatives
US4400545A (en) * 1980-10-08 1983-08-23 Fritzsche Dodge & Olcott Inc. Alicyclic ketone and alcohol derivatives
US4432378A (en) * 1980-01-30 1984-02-21 Fritzsche, Dodge & Olcott, Inc. Substituted cyclohexane derivatives
US4585582A (en) * 1985-03-08 1986-04-29 International Flavors & Fragrances Inc. Perfumery uses of 2-n-pentyl-2-cyclohexen-1-one
US4808409A (en) * 1984-08-16 1989-02-28 Board Of Trustees, University Of Illinois Low cariogenic sweetening agents
CN1056826C (zh) * 1995-07-04 2000-09-27 云南省烟草工业研究所 大豆－5,8－二烯－4－酮的制备方法及应用
US20040059163A1 (en) * 2002-09-19 2004-03-25 Dietmar Schatkowski Method for the preparation of trimethylcyclohexyl-alkan-3-ols containing a high proportion of trans isomers
EP2072083A1 (de) * 2007-12-19 2009-06-24 Symrise GmbH & Co. KG Verwendung von 2,4'-Dimethyl-propiophenon als Riechstoff
US20120288448A1 (en) * 2011-05-10 2012-11-15 Nwachukwu Chisomaga Ugochi Sprayable Compositions For Reducing Particulates In The Air
US10252210B2 (en) 2011-05-10 2019-04-09 The Procter & Gamble Company Methods for reducing particulates in the air

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3231189A1 (de) * 1982-08-21 1984-02-23 Basf Ag, 6700 Ludwigshafen Verfahren zur herstellung von verbindungen der megastigman-reihe sowie neue zwischenprodukte fuer diese synthese
WO1998001121A1 (fr) * 1996-07-05 1998-01-15 Shionogi & Co., Ltd. Antagoniste des canaux calciques de type p/q

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3268589A (en) * 1963-05-29 1966-08-23 Reynolds Tobacco Co R Process for preparing 4-(2-butenylidene)-3, 5, 5-trimethyl-2-cyclohexene-1-one
US3746010A (en) * 1972-08-11 1973-07-17 Reynolds Tobacco Co R Tobacco product
US3881025A (en) * 1971-03-09 1975-04-29 Firmenich & Cie Aromatic compositions
US3927107A (en) * 1972-10-26 1975-12-16 Firmenich & Cie 2,6,6-Trimethyl-1-alkenoyl-cyclohexenones
US4076854A (en) * 1977-03-03 1978-02-28 International Flavors & Fragrances Inc. Flavoring with a cyclohexadiene derivative
US4084009A (en) * 1977-03-03 1978-04-11 International Flavors & Fragrances Inc. Flavoring with a hydroxy cyclohexenone derivative

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1454047A (fr) * 1965-08-20 1966-07-22 Reynolds Tobacco Co R Dérivé de buténylidène-triméthyl-cyclohexénone utile comme additif pour le tabac et son procédé de préparation
DE1692938A1 (de) 1966-03-05 1972-03-16 Reemtsma H F & Ph Verfahren zur Beeinflussung der geschmacklichen Eigenschaften des Tabakrauches
CH648015A5 (de) * 1977-03-28 1985-02-28 Givaudan & Cie Sa Cyclohexenonderivate mit riech- und/oder geschmackstoffeigenschaften.

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3268589A (en) * 1963-05-29 1966-08-23 Reynolds Tobacco Co R Process for preparing 4-(2-butenylidene)-3, 5, 5-trimethyl-2-cyclohexene-1-one
US3881025A (en) * 1971-03-09 1975-04-29 Firmenich & Cie Aromatic compositions
US3746010A (en) * 1972-08-11 1973-07-17 Reynolds Tobacco Co R Tobacco product
US3927107A (en) * 1972-10-26 1975-12-16 Firmenich & Cie 2,6,6-Trimethyl-1-alkenoyl-cyclohexenones
US4076854A (en) * 1977-03-03 1978-02-28 International Flavors & Fragrances Inc. Flavoring with a cyclohexadiene derivative
US4084009A (en) * 1977-03-03 1978-04-11 International Flavors & Fragrances Inc. Flavoring with a hydroxy cyclohexenone derivative

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4313856A (en) * 1977-03-28 1982-02-02 Givaudan Corporation Perfume compositions containing oxygenated ionone derivatives
US4352943A (en) * 1977-03-28 1982-10-05 Givaudan Corporation 3-Butadienyl-2,4,4-trimethylcyclohex-2-enone and derivatives thereof
US4363331A (en) * 1977-03-28 1982-12-14 Givaudan Corporation Tobacco products containing oxygenated ionone derivatives
US4311718A (en) * 1977-03-28 1982-01-19 Givaudan Corporation Flavoring with 2,4,4-trimethyl-3-(buta-1,3-dienyl)cyclohex-2-en-one
US4326996A (en) * 1980-01-30 1982-04-27 Fritzsche Dodge & Olcott Inc. Fragrance composition comprising substituted cyclohexane derivatives
US4432378A (en) * 1980-01-30 1984-02-21 Fritzsche, Dodge & Olcott, Inc. Substituted cyclohexane derivatives
US4326997A (en) * 1980-10-08 1982-04-27 Fritzsche Dodge & Olcott Inc. Fragrance compositions of alicyclic ketone and alcohol derivatives
US4400545A (en) * 1980-10-08 1983-08-23 Fritzsche Dodge & Olcott Inc. Alicyclic ketone and alcohol derivatives
US4808409A (en) * 1984-08-16 1989-02-28 Board Of Trustees, University Of Illinois Low cariogenic sweetening agents
US4585582A (en) * 1985-03-08 1986-04-29 International Flavors & Fragrances Inc. Perfumery uses of 2-n-pentyl-2-cyclohexen-1-one
CN1056826C (zh) * 1995-07-04 2000-09-27 云南省烟草工业研究所 大豆－5,8－二烯－4－酮的制备方法及应用
US20040059163A1 (en) * 2002-09-19 2004-03-25 Dietmar Schatkowski Method for the preparation of trimethylcyclohexyl-alkan-3-ols containing a high proportion of trans isomers
US7019181B2 (en) * 2002-09-19 2006-03-28 Symrise Gmbh & Co. Kg Method for the preparation of trimethylcyclohexyl-alkan-3-ols containing a high proportion of trans isomers
EP2072083A1 (de) * 2007-12-19 2009-06-24 Symrise GmbH & Co. KG Verwendung von 2,4'-Dimethyl-propiophenon als Riechstoff
US20090162308A1 (en) * 2007-12-19 2009-06-25 Symrise Gmbh & Co. Kg Use of 2,4'-dimethylpropiophenone as a fragrance substance
US20120288448A1 (en) * 2011-05-10 2012-11-15 Nwachukwu Chisomaga Ugochi Sprayable Compositions For Reducing Particulates In The Air
US10252210B2 (en) 2011-05-10 2019-04-09 The Procter & Gamble Company Methods for reducing particulates in the air

Also Published As

Publication number Publication date
JPS5368754A (en) 1978-06-19
CH633508A5 (de) 1982-12-15
DE2752787A1 (de) 1978-05-24
NL7712928A (nl) 1978-05-25
GB1591098A (en) 1981-06-17
FR2371412A1 (fr) 1978-06-16

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